Mixed packet photographic emulsions



United States Patent "ic 298,794

Patented Jan. 4, 1955 colloid carrier. The couplers are incorporated inthe emulsion by dissolving them in a substantially water- 2,698,794insoluble slolvent fgr tars coupler, and tilispersinlg thistlfllt1 n ine atin n in it to atino-siver MIXED PACKET PHOTOGRAPHIC EMULSIONS 5 3,5, a a g a ge a 1 e The silver halide used in these emulsions may beoptically sensitized, and ordinarily two or more emulsions sensitive todiiferent regions of the visible spectrum will be employed.

Application April 1950 Serial 156 066 10 The following couplers aresuitable for use according to my invention:

11 Claims. l- CYAN COUPLERS This invention relates to color photographyand par- 15 ticularly to mixed packet photographic emulsions. Cl- -NHOO-CHz-O-QOsHn There have been many prior suggestions of mixed grainphotographic emulsions, that is, photographic systems $511 in whichdifferently sensitized silver halide grains are incorporated in a singlephotographic emulsion layer and i used to produce ditferently coloredphotographic images in the layer. Mixed grain systems have a number ofady p ly 0 0-5- vantages, chief among which is the simplicity of coatingmethylphenol a single emulsion layer rather than several layers. Other0H advantages are the improved definition obtained by having thedifferently sensitized particles juxtaposed in a 01- NHC mam-000,11

single layer, and the simplification of processing which E is generallyobtained. CH? 5 6 Prior mixed grain photographic methods have not beensuccessful either because it was impossible to secure color separationwith them, that is, effectively to prevent color formation aroundunexposed silver halide grains, or be- 2-[a-(2,4'-tert-amylphenoxy)-n-butyrylamino]4,6-

cause the colored particles formed in the process were -7 too grainy. OH

It is therefore an object of the present invention to provide a methodand sensitive material for mixed packet O color photography according towhich difficulties in the I prior art are overcome and a practicalresult is achieved. CH 02115 By mixed packet I mean a process or anemulsion in 3 which differently color-sensitive silver halide grainshav- 9 a ing color-formers associated therewith are incorporated in 1 asingle Photographic layer for the P p of producing2-[a-(4-tert.-amylphenoxy)-n-butyrylamino1-4-chlor0- differently coloredphotographic images in that layer by 5-methy 'D a single exposure. on

Thefse objects are acgomplished by first gislpgrsing 1a I colorormingcompoun in a peptize si ver a i e emu sion, preferably a gelatino-silverhalide emulsion. The CONH (CH2)! 0 emulsion may contain the normalamount of gelatin, or a 1 lower amount than usual may be present. Forexample,

the gelatin content may be from 4 to 200 grams or more Leopold Godowsky,Westport, Conn., assignor to Eastman Kodak Company, Rochester, N. Y., acorporation of New Jersey per 100 grams of silver halide. The emulsioncontaining the coupler dispersion is then mixed with a suitablenaphthamlde water-dispersible polymer which does not react with gela- OHtin, and to the mixture there is added a solution of a I polymericpacket-forming component. Two or more of CONH(CH2)4O 05H the resultingpacket dispersions which contain silver halide sensitized to differentspectral regions, are then mixed with additional gelatin or anotherwater-soluble polymer 05H to form the mixed packet emulsion, preferablyby adding G1 the gelatin or polymer to each packet dispersion separatelybefore mixing them.1-hydroxy-4-chloro-2-[6-(2',4'-di-tert.-amy1phenoxy)-n-buty1]- Theaccompanying drawing is a flow sheet illustrating aphthamlde the1Vslteps 1n rrtry process. th f 1 h rd 1 MAGENTA COUPLERS y mven 1cninvo ves e use 0 a s1 ver a1 e emu sion containing a non-diffusingcolor-forming compound NE 000mm or coupler which is reactive with theoxidation product 0 of a primary aromatic amino developing agent to forma dye image. These couplers are preferably incorporated in the emulsionas described in Jelley and Vittum U. S. Patent 2,322,027, but may bedirectly dispersed in the 1-pheny1-3-palmltoylamino-5-pyrazoloneN=C-NHOOC 1 0 Cs n (Iii-CH2 0 1- [p- (p'-tert.-butylphenoxy) -phenyl -3-[mp-tert-amylphenoxy) benzoylamino -5-pyrazolone 1-( p-[p-tert.-butylphenoxy]-phenyl)-3-(m-[p-toluenesulfonylamino]-benzoylamino-o-pyrazolone) YELLOW COUPLERSN-(p-benzoylacetuminobenzenesulphonyl)-N-(n-amy1- p-tert.-amy1am'1ine6-0 euro onnQ-sm-st-mmn-G N- p-benzoylacetnminobenzenesulphonyl -N-('y-phenylpropyl) -aniline O4: 0 onto ONHQSOz-T-OOHQ N-p-benzoylacetaminobenzenesulphonyl) -N-benzyl-p-to1uidine O0 0 ornoONHO-Sm-n- CHmO N-(p-benzoylacetaminobenzenesulphonyl) -N-('y-pl1euylpropyl) ptert.-amy1anili11e -o 0 01120 ONHO-SOHTT-(CHQs-O N-(p-benzoylacetaminobenzenesulphonyl -N- ('y-phenylpropyl)-(o)-, (m), or(p)-toluidine After making the dispersion of coupler in gelatinosilverhalide emulsion, the dispersion is added to a water solution of awater-soluble polymer or water-soluble salt of a polymeric materialcontaining salt-forming acid groups, such as the copolymer ofmethacrylic acid and methyl-tt-methacrylate (Minsk, Weyerts and McDowellU. S. Patent 2,391,181) algin (alkali metal salt of polymericd-mannuronic acid), carboxy methyl cellulose (Collins, Freeman andAnthonisen U. S. Patent 2,278,612), and cellulose sulfate (BelgianPatent 448,249). The Water-soluble polymer is mixed with the gelatin ofthe dispersion and acts as a modifying agent, so that small packets,each containing appropriately sensitized silver halide and color-formingcoupler, can be formed.

To the mixture of dispersion and water-soluble polymer or salt,mentioned above, .there isthen added, preferably with stirring, anaqueous solution of a polymeric packet-forming component or gelatinreactant, or vice versa. The polymeric, packet-forming componentconsists of a polymeric carbon chain having recurring phenyl groups andcarboxyl groups, and preferably also carboxylic acid amide groups orimide groups or both and is used as the water-soluble salt, such as theammonium, sodium, potassium or lithium salt. The polymericpacket-forming component is preferably an inter-polymer of styrene andan o B-UHSHUIl'fiEEd carboxylic acid, part of whose carboxyl groups mayhave been converted to amide or imide derivatives or both, such asinterpolymers of styrene-maleic acid, styrene-acrylic acid,styrenemethacrylic acid or styrene-itaeonic acid.

The mixture of coupler-silver halide dispersion, watersoluble polymerand polymeric packet-forming component now consists of particles orpackets of gelatin, associate with polymeric packet-forming component,containing silver halide and coupler, the packets being dispersed in anaqueous medium containing additional gelatin or another film-formingwater-soluble polymer. This is finally mixed with at least one othersimilarly made packet dispersion containing differently-sensitizedsilver halide and a different coupler to form the finished mixed grainemulsion. The finished emulsion is then ready for coating on a suitablesupport, such as glass, cellulose ester, or paper.

In the preparation of the system described above, that is, gelatin,water-soluble polymer, and packet-forming component, the ingredientsmust be present in a fairly QCfillltr') ratio. If the gelatin is presentin approximately 0.7% aqueous solution (an appropriate concentration formaking an emulsion), then the Water-soluble polymer should be present inan amount from about 1 to 2 times that of the gelatin, and thepacket-forming component should be present in an amount from 0.01 to 0.5times that of the gelatin. Within these ranges the three-componentsystems exhibit a definite degree of optical turbidity. If thisturbidity is measured in optical density per cm. of mixture at 30 C.,using orange-colored light, of about 5800 A. U., the optical density isgreater 0.05, and is generally of the order of 0.1.

Suitable polymers of styrene with maleic acid or its derivatives arerepresented by the following formula:

I solo 0 its 2/ Suitable polymers of styrene with acrylic acid or itsderivatives may be represented by the following formula:

R R R R R CHrCH-CHr-QFCHz--CHz--Cflr-CHr- 0 CO CO (30 l Y OH Z In eachformula H NH2 NHR' NRTz R=hydrogen CH3 CzHs R=alkyl of less than sixcarbon atoms or aryl Z=NH NR OH groups on each carbon atom to which Z isattached.

n=the number of units in the polymer chain.

It will be understood that the above structural formulas areillustrative only, and are not limiting as to ratios and unitarrangements of constituents.

The polymeric packet-forming components of the first structural formulaabove may be prepared by forming an interpolymer of styrene and maleicanhydride, and then treating the polymer with ammonia, a primary orsecondary amine, or water, as indicated by the following formula usingammonia:

Formation of these polymers is described in Condo, Krister and LundquistU. S. Patent 2,286,062 and McDowell and Kenyon U. S. Patent 2,313,565.

Interpolymers of styrene and acrylic anhydride or a-methacrylicanhydride may be used instead of the interpolymer of styrene and maleicanhydride, as indicated by the following formula using ammonia:

Imide groups along the polymer chain may result from the interaction ofadjacent amide groups or an amide and a carboxyl group.

These polymers may also be prepared by direct polymerization, e. g.,styrene, acrylamide or N-substituted acrylamide, acrylic acid; orstyrene, maleamic acid or N-substituted maleamic acid.

In order to ascertain'the packet-forming components which are suitablefor use in my process, the following test may be made:

A solution or dispersion of the polymeric compound to be tested,gelatin, and the sodium salt of methylmethacrylate-methacrylic acidpolymer is made up in water so that the final concentrations aregelatin, 0.7%; methylmethacrylate-methacrylic acid salt, 1.67 times theamount of gelatin; and polymeric compound, 0.1 to 0.5 times the amountof gelatin. The gelatin is a deashed calfskin gelatin having anisoelectric point of approximately 4.8. The polymeric compound is addedas an approximately 2% solution in ammonium hydroxide of pH 7.5. Whenvigorously stirred, this mixture is characterized by its ability toscatter or diffuse light transmitted through it. With polymericcompounds suitable for my process, the mixture must exhibit an opticaldensity of at least 0.05 per centimeter of mixture, when measured at 30C. wlth orange-colored light of approximately 5800 Angstrom units wavelength.

The packet-forming components were prepared as follows:

Example 1.Styrene-maleic anhydride interpolymer Into a 12-liter allglass reflux outfit equipped for an hydrous conditions the followingwere measured:

234 gm. distilled styrene 220.5 gm. maleic anhydride 3188 ml. drybenzene 4.25 gm. benzoyl peroxide Example 2.-P0lystyrene-maleamic acidpolymer 50 gm. of polystyrenemaleic anhydride were added gradually to250 ml. of 28% ammonium hydroxide 111 a 500 ml. Erlenmeyer flask withstirring from a mixer to form a slurry. After stirring for eighteenhours at room temperature a viscous, clear colorless dope was obtained.300 gm. of this dope was diluted to approximately 2% solids with waterand 48% hydrobromic acid was added to it until it was -just acid toCongo red. The solid that was formed was separated by filtration, andleached with absolute alcohol until the wash solutions were bromidefree. The solids were put to dry in an oven at 60 C.

20 gm. of the solid were doped to form a 5% dope by weight in water madealkaline with 13 ml. of 20% sodium hydroxide. pH=8.63.

Example3.Polystyrene-maleamic acid ammonium salt The following reagentswere put to reflux in an all glass reflux outfit equipped with amechanical stirrer. Conditions were maintained anhydrous by calciumchloride tubes on all openings to the atmosphere.

49 gm. maleic anhydride (Eastman white label) 52 gm. distilled styrene1500 ml. dry toluene 2.0 gm. benzoyl peroxide The reaction mixture washeated for 2% hours on a steam bath without stirring and then allowed tocool to room temperature. A small sample of the solids was withdrawn,washed with fresh benzene, and put to dry for analysis and viscositypurposes.

The stirrer was turned on and dry ammonia was bubbled into the reactionmixture continuously for 3 /2 hours. During this time the temperaturewithin the reaction mixture rose from a starting temperature of 23 C. to45 C. and then returned to 23 C. The solids were filtered off on aBiichner funnel, washed with toluene, and put to dry in a vacuum oven at60 C. over night.

The residual toluene was then extracted with absolute alcohol bystirring the product with 23 1. portions of absolute ethyl alcohol andfiltering onto a Biichner funnel. The product was then dried as above.

Forty grams of the polymer were gradually added to 200 ml. of water inan Erlenmeyer flask with mechanical stirring. The solution was keptslightly alkaline by the portion-wise addition of 28% NH4OH. The pH wasnever allowed to exceed eight. A clear colorless dope was obtained whichwas then adjusted to 15% solids by weight by the addition of distilledwater. The pH of this solution was 6.38.

Example 4.-Amm0nium salt of stryene-maleic acid interpolymer 10 gm. of astyrene-maleic anhydride interpolymer were heated with 200 ml. ofdistilled water on a steam bath for 6 hours and then left at roomtemperature for 65 hours. After this period of hydrolysis, 28% NH4OH wasadded to the mixture portion-wise while it was mechanically stirred,using no more ammonium hydroxide than was necessary to effect solution.The solution was then diluted to 400 g. total weight with distilledwater. The pH of the solution was 6.34.

Example.5.Sodium salt of styrene-maleic acid interpolymer The procedurewas similar to the above example except that 10% sodium hydroxide wasused to effect solution of the hydrolyzed styrene-maleic anhydrideinterpolymer. The pH of the final solution was 8.16.

Example 6.Styrene-acrylic anhydride copolymer The following were heatedin an all glass reflux outfit on a steam bath under anhydrous conditionsfor 24 hours:

42 gm. distilled acrylic anhydride 35 gm. distilled styrene 500 ml. dry1,4-dioxane 0.8 ml. 30% H202 The reaction mixture was shaken frequently.During the first hour the mixture began to become cloudy; shortly afterthis period, the mixture became very cloudy and set to a gel. Aftercooling to room temperature, the solids were broken up, separated byfiltration and washed with dry dioxane. The polymer was dried in vacuumdesiccator under constant water pump vacuum, with a calcium chloridetube in the vacuum line.

Preparation of the styrene-acrylic acid-acrylamide polymer was carriedout similar to the preparation of the polystyrenemaleamic acid polymerin aqueous ammonium hydroxide, only using the above intermediate.Example 7.Il/IethacryZic anhydride-styrene interpolymer 61.6 gm.distilled rnethacrylic anhydride 41.6 gm. distilled styrene 1.0'nil. 30%H202 600ml. dry 1,4 dioxane The solution gelled after the first hour andhalf of heating. When the reaction mixture had cooled to roomtemperature after the 16 hour heating period, the gel was manuallybroken up and washed with dry 1,4-dioxane in a Biichner fur product wasdried.

The preparation or": the styrene methacrylic acid, methacrylamidepolymer as carried out exactly similar to the preparation oi thepolystyrene-malearnic acid polymer in ammonium hydroxide.

Example 8.-lvla1cic anhydride: styrene: vinyl acetate imerpolymer Thefollowing were ut in a resin reaction flask equipped with a refluxcondenser and mechanical stirrer:

.-[Malermzic acidnszyreiiemfizyl acetate ifllifpolymer Exalizpie 9 Fiftygrains of the styrenewinyl acetatc-malec anhy dride interpolymer(Example 8) w .e "(l(i'l o 28 per cent ammonium hydroxide i mixture wasstirred for id hours, during which time solution occurred a viscous dopewas obtained This was dil ted to 1220 g .335 with distilled water, 1 nga 5 per cent solution. Two hundred ms of the above dope were diluted to750 cc. with dist led water and t1 -n made acid to Congo red withhydrobromic d. The precipitate was filtered and "then extracted withabsolute ethyl alcohol until bromide-free. The product was then dried invacuum. The yield was 7 grams. This was dispersed by stirring in watercontaining ammonium hydroxide.

Example Iri a Jaime aizliytiride:styreire:bmy! acryl'ate interpoz'yliterThe following were put in an all-glass reflux outfit equipped foranhydrous conditions on a steam bath to reflux for 2 hours:

36.4 grams distilled styrene 49.0' grams maleic anhydride 19.2 gramsdistilled butyl acrylatc 1.0 gram benzoyl peroxide 750 ml. dry benzeneWhen the reaction was completed. t I ture was cooled to roomtemperature. The result! cipitate was isolated by filtration on :r Bichner washed with dry benzene, and put to dry i desiccator under couS*'t water pump vac The yield was 76.6 grams. inherent visco y, t r (SeeCragg, J. ColloidScience, vol. 1, page 261, 31946, for description ofinherent viscosity.)

Example 11.Ma!eamic aciekbutyl acrylazeuryrcne interpolymer Forty gramsof the interpolymer of styrene-butyl acrylate and maleic anhydrideintcrpolyrner (Example 10) were added with stirring to 269 c. of 28 percent ammonium hydroxide kept chilled in an ice bath. In minutes aviscous dope was obtained and 100 cc. of water by filtration and washedwith water 1 nil bi wereadded. The reaction mixture was stirred for 2.hours with continued chilling. diluted. to 1600 grams and then the pHwas adjusted to 7.9 with 6-N sulfuric acid. Four hundred grams of thisdo e were diluted to 800 cc. with distilled water and made acid to Congored with 20 per cent hydrobromic acid. The precipitate was filtered andextracted with absolute ethyl alcohol until bromide-free. The productwas then dried in vacuum. The yield was 11.5 grams. This was dispersedas described in Example 9. I

Example ]2.--Styrei1e N-butyl maleamic acid interpolymer Forty andfourtenths grams of styrene-maleic anhydride interpolyrner (inherentviscosity, 0.68) were dispersed with shaking 4C4 cc. of dry methyl ethylltetone. To the dope was added with stirring a solution of 14.6 grams ofn-butylamine in 404 cc. of dry methyl ethyl liC-iOllfii. There wasinstant precipitation. The mixture was well shaken and left at roomtemperature for .7 hours. The polymer had then precipitated as a cakewhich was broken up and to the mixture was added 50 cc. of 28 per centammonium hydroxide. The eaction mixture was then allowed to'stand for 5-hours. The precipitate was then filtered, reexlract d with methyl ethylketone and dried in vacuum. The yield was 64 urns.

Forty grams of this polymer were dispersed in 1000 cc. of distilledwater to which had been added cc. of 28 per cent ammonium hydroxide.Solution occurred. The dope was diluted to 1 00 grams, in: ting concentrtion of 2.5 per cent in solids. The pl-i las 9.0.

To isolate the acid form of the polyn e 400 grams of .'s dope dilutedwith an equal part of water were made red to Congo red with 20 per centhydrobromic acid. The precipitate was '"ltered, extracted with wateruntil died in vacuum. he yield was 7 tion of this prcci was redispersedin Wu. y .no addition of ammonium hydroxide, it was found to yieldpackets.

Example I3.--POZystyrene-N-dietlzyl maleic acid olated nude-free. Theproduct was then dried in a vacuum desiccator under constant Water pumpvacuum.

To prepare the ammonium salt of the polystyrene 1*- diethyl maleamicacid, 10 grams of the acid polymer were added to 75 ml. of w ter 1thstirring by a. mixer. Twenty-eight per cent NHAOH was added portionwiseto keep the pH at about 3. After 12 hours stirri g 2. light amber dopewas obtained. This dope was filtered and diluted to 6.66 per centsolids, pH 8.33.

Example 14.C0poiymer 0 styrenemcry[amide:acrylic acid The following wereput in an all-glass reflux outfit:

52 grams styrene 5 g ams acrylemide 36 grams acrylic acid 1.225 gramsbenzoyl peroxide 367.5 grams absolute ethyl alcohol Example 15 Separatered-sensitive and green-sensitive silver bromoiodide emulsions were madecontaining 33 grams of gelatin per grams of silver halide.

The smooth dope obtained was A cyan Coupler dispersion was made bydissolving 4.375 grams of the coupler2-[ot-(2,4-di-tert.-arnylphenoxy)-n-butyrylamino]-4,6-dichloro--methylphenol and 0.27 gram of dioctyl hydroquinone in 5 cc. of n-butylphthalate at 150 C. adding the solution to 5 cc. of a 5% solution ofAlkanol B dispersing agent in 25 cc. of gelatin solution, and dispersingit therein.

A magenta coupler dispersion was made by dlSSOlVlIlg 2.75 grams of thecoupler l-(p-p'-tert.-butyl-phenoxyphenyl) 3[m.-(p-tert.-amylphenoxy)benzoylaminol- S-pyrazolone and 0.21 gram ofdioctyl hydroquinone 1n 7.9 cc. of n-butylphthalate at 165 0., addingthe solution to 5 cc. of a 5% solution of Alkanol B in 25 cc. of 10%gelatin solution, and dispersing it therein.

Six grams of the red-sensitive emulsion containing 0.4 gram of silverhalide and 0.13 gram of gelatin were added to 8 grams of the cyancoupler dispersion and mixed with a fast stirrer for 10 minutes. Twelvecc. of a 10% solution of a copolymer of methacrylic acid andmethyl-a-methacrylate (sodium salt) were mixed with 100 cc. of distilledwater. The emulsion-coupler dispersion was added to the copolymersolution, and this was stirred for 10 minutes more. To this mixturethere were added 4 cc. of a 0.5% solution of the ammonium salt ofstyrenemaleamic acid polymer, and the Whole dispers1on was stirred at42" C. for one hour. Then 50 cc. of an 18% solution of gelatin wereadded and mixed.

A similar dispersion was made using 6 grams of the green-sensitiveemulsion containing 0.4 gram of silver halide and 0.13 gram of gelatin,and 8 grams of the magenta coupler dispersion instead of thered-sensitive emulsion and cyan coupler.

The two final dispersions were mixed together and coated, and afterexposure and development in a p-phenylene-diamine type color developer,gave satisfactory cyan and magenta images in the portions exposed to redand green light, respectively.

A three-color emulsion was made as follows:

Example 16 A yellow-forming coupler dispersion was made by firstdissolving 5 grams of the coupler N-(p-benzoyl acetamino benzenesulfonyl)-N-('y-phenylpropyl)-p-toluidine and 0.21 gram of dioctylhydroquinone in 8 grams of dibutyl phthalate at 140150 C. This solutionwas added to 25 grams of 10% gelatin solution containing 5 cc. of a 5%solution of Alkanol B dispersing agent and the mixture stirred for fiveminutes. Six grams of a concentrated gelatino-silver bromoiodideemulsion .containing 2.04'

grams of silver halide and 0.095 gram of gelatin were then added to 8grams of the coupler dispersion and the mixture stirred for minutes at40 C. The mixture was then added to 12 cc. of a 10% solution of acopolymer of methacrylic acid and methyl-wmethacrylate (sodium salt) in100 cc. of water which had been stirred at 40 C. for 10 minutes. To thismixture there were added 5 cc. of a 0.5% solution of the ammonium saltof styrenemaleamic acid polymer and the whole dispersion was stirred for12 minutes more. The mixture was then added to 50 grams of an 18%gelatin solution.

A cyan-forming coupler dispersion was made by dissolving 3.5 grams ofthe coupler 2-[a-(2',4-tert.-amylphenoxy)-n-butyryl amino],4,6-dichloro-5-methylphenol and 0.21 gram of dioctyl hydroquinone in 8grams of dibutyl phthalate at 140150 C. This solution wasadded to 25grams of a 10% solution of gelatin containing 5 cc. of a 5% solution ofAlkanol B and was stirred for five minutes. added to 5.25 grams of ared-sensitive 95 mole per cent chloride, silver chlorobromide emulsioncontaining 1.24 grams of silver halide and 0.43 gram of gelatin,prepared by adding 5 milligrams'of the red sensitizer, 5 [4-(3-ethyl- 2-(3 -benzothiazolylidene) -2-butenylidene1 -3-n-heptyllphenyl-Z-thiohydantoin (U. S. Patent 2,282,116) in 8 cc; of acetone to66 grams of the emulsion, and the mixture was stirred for 15 minutes at40 C. The mixture was then added to 12 grams of a 10% solution of acopolymer of methacrylic acid and methyl-a-methacrylate (sodium salt) in100 cc. of water which had been stirred for 15 minutes at 40 C. Themixture was stirred for 10 minutes at 40 C. and to it was added 5 cc. ofa 0.5 solution of the ammonium salt of styrene-maleamic acid polymer andthe mixture was stirred for 10 minutes more.

Eight grams of this coupler dispersion were.

10 It was then added to 50 cc. of an 18% gelatin solution and mixed.

A magenta-forming coupler dispersion was made by first dissolving 2.75grams of the coupler, 1-[p-(p'-tert.- butyl-phenoxyl) phenyl] 3[m-(p-tert.- amylphenoxy)- benzoylamino]-5-pyrazolone and 0.21 gram ofdioctohydroquinone in eight grams of dibutyl phthalate at C. Thissolution was added to 25 cc. ofa 10% gelatin solution containing 5 cc.of a 5% solution of Alkanol B and was stirred for five minutes. Eightgrams of this dispersion were added to 5.25 grams of a greensensitive 95mole per cent chloride, silver chlorobromide emulsion containing 1.24grams of silver halide and 0.43 gram of gelatin made by sensitizing 66grams of the emulsion with 7 /2 milligrams of the green-sensitizer5-[(1-ethyl-2-(3 )-ot-naphthoxazolylidene)-ethylidenel 3 nheptyll-phenyl-2-thiohydantoin (U. S. Patent 2,282,116) in 10 cc.'ofmethanol. This mixture was then added to a solution of a copolymer ofmethacrylic acid and methyl-amethacrylate (sodium salt) and a solutionof the ammonium salt of styrene-maleamic acid polymer in the same way asthe red-sensitive emulsion described above.

To produce a three-color coating, 60 grams of each of theblue-sensitive, green-sensitive and red-sensitive components were mixedwith stirring. The mixture was then coated in the usual manner on apaper support and dried. After exposure and development in a developingsolution containing 2-amino-5-diethyl amino toluene hydrochloride as thedeveloping agent, colored images complementary to the color of theexposing light were formed in the emulsion.

I claim:

1. A light-sensitive mixed packet photographic emulsion comprisingpackets or discrete particles of gelatin reacted with a water-solublesalt of an interpolymer of styrene and an a,,8-unsaturated carboxylicacid, said particles or packets containing a non-difiusing color-formingcompound capable of reacting with the oxidation product of a primaryaromatic amino developing agent on photographic development, and silverhalide sensitive to at least one region but less than all regions of thevisible spectrum, and at least one separate set of packets or dis creteparticles of gelatin reacted with said interpolymer containing anon-diffusing color-forming compound dilferent from said first mentionedcolor-forming compound and silver halide sensitive to a region of thevisible spectrum diiferent from that to which said first mentionedsilver halide is sensitive, the sensitive and color-forming ingredientsbeing within the respective packets or discrete particles and all ofsaid packets or discrete particles being dispersed in gelatin havingmixed therewith a watersoluble salt of a polymer selected from the classconsisting of methylmethacrylate-methacrylic acid copolymer, algin,carboxy methyl cellulose and cellulose sulfate.

2. A light-sensitive mixed packet photographic emulsion comprisingpackets or discrete particles of gelatin reacted with the ammonium saltof a styrene-maleamic acid polymer, said particles or packets containinga nondiffusing color-forming compound capable of reacting with theoxidation product of a primary aromatic amino developing agent onphotographic development, and silver halide sensitive to at least oneregion but less than all regions of the visible spectrum and at leastone separate set of packets or discrete particles of gelatin reactedwith said polymer, containing a non-difiusing color-forming compounddiiferent from said first mentioned color-forming'compound and silverhalide sensitive to a region of the visible spectrum different from thatto which said first mentioned silver halide is sensitive, the sensitiveand color-forming ingredients being within the respective packets ordiscrete particles and all of said packets being dispersed in gelatinhaving mixed therewith the sodium salt of methylmethacrylate methacrylicacid copolymer.

3. A photographic element comprising a support having thereon a singlelight-sensitive water-permeable colloid layer containing (1) packets ordiscrete particles of gelatln reacted with the ammonium salt of astyrene-maleamic acid polymer, said particles or packets containing anondiflusing yellow-forming coupler and blue-sensitive silver halide,(2) packets or discrete particles of gelatin reacted with the ammoniumsalt of a styrene-maleamic acid polymer, said particles or packetscontaining a non-diffusing magenta-forming coupler and green-sensitivesilver halide, and (3) packets or discrete particles of gelatin reactedwith the ammonium salt of a styrene-maleamic acid polymer, saidparticles or packets containing a nondut'using cyan-rorming coupler andred-sensitive silver halide, and said colloid layer having mixedtherewith the sodium salt or" methylmethacrylate-methacrylic acidcopolymer.

4. lbs method or making a mixed packet photographic emulsion whichcomprises dispersing in a gelatino-sllver halide emulsion sensitive toat least one but less than all regions of the visible spectrum, anon-dilrusing colorforming compound capable of reacting with theoxidation product of a primary aromatic amino developing agent onphotographic development to form a dispersion or' the color-formingcompound in the emulsion, mixing said dispersion with rrom about onepart to about two parts per part of gelatin in said emulsion, of awater-soluble salt or' a polymer selected from the class consisting ofmethylmethacrylate-methacrylic acid copolyrner, algin, carboxy methylcellulose and cellulose sulrate, adding to the mixture of dispersion andpolymer slowly and with stirring a solution or a water-soluble salt ofan interpolymer of styrene, said interpolymer containing at least acarboxylic acid group of the groups selected item the class consistingof carboxylic acid and carboxylic acid amide groups to form a dispersionof particles of gelatin, water-soluble salt of styrene interpolymer andsilver halide, containing the color-forming compound, forming in thesame way as said last-mentioned dispersion at least one other dispersionof particles of gelatin, water-soluble salt of styrene mt rpolymer,diilereht non-diffusing colorforming compound and silver halidesensitive to a region of the visible spectrum different from that towhich said first-mentioned silver halide is sensitive, in each of saiddispersions said water-soluble polymer beng used in an amount from about1 to about 2 times the amount of gelatin, and said water-soluble salt ofstyrene interpolymer being used in an amount less than about one-ha theamount of gelatin, and mixing said dispersions of particles with agelatin solution.

5. The method of making a mixed packet photographic emulsion whichcomprises mixing a non-di'rrusing colortorming compound capable ofreacting with the oxidation product of a primary aromatic aminodeveloping agent on photographic development, with a substantiallyWater-insoluble solvent for said color-forming compound to form asolution of the color-forming compound in the solvent, dispel 'ng thesolution in a gelatino-silver halide emulsion sensitive to at least onebut less than all regions of the visible spectrum, mixing saiddispersion with from about one part to about two parts per part ofgelatin in said emulsion, of a water-soluble salt of a polymer se lectedfrom the class consisting of methylmethacrylatemethacrylic acidcopolymer, algin, carboxy methyl cellulose and cellulose sulfate, addingto the mixture of dispersion and polymer slowly and with stirring asolution of a water-soluble salt of an interpolymer of styrene, saidinterpolymer containing at least a carboxylic acid group of the groupsselected from the class consisting of carboxylic acid and carboxylicacid amide groups to form a dispersion of particles of gelatin,water-soluble salt of styrene inter-polymer and silver halide,containing the color-forming compound, forming in the same way as saidlast-mentioned dispersion at least one other dispersion of particles ofgelatin, Water-soluble salt of styrene interpolymer, diiferentnon-diffusing color-forming compound and silver halide sensitive to aregion or" the visible spectrum different from that to which saidfirst-mentioned silver halide is sensitive, in each of said dispersionssaid water-soluble polymer being used in an amount from about 1 to about2 times the amount of gelatin, and said water-soluble salt of styreneinterpolymer being used in an amount less than about one-half the amountof gelatin, and mixing said dispersions of particles with a gelatinsolution.

sphic mixed packet dispersion, the continuous phase comprising'anaqueous colloidal binder and the disperse phase comprising at least twodilferently light-sensitive sets of packets or discrete particles, eachpacket of any one set itself containing dispersed therein silver halidegrains sensitized to one of the primary regions of the visible spectrumand also containing dispersed therein non-diffusing color-formingcompound capable of reacting with the oxidation product of a primar.aromatic amino develo in" a ent on hoto ra hic development, theparticles of any one set being formed when a water-soluble salt of astyrene interpolymcr containing carboxylic acid groups is added in thepresence or a water-soluble salt of methyl methacrylate-methacrylicacid, 0 a silver halide dispersion peptized by gela- Llii, the styreneintcrpolymer-gelatin combination which forms the continuous phase or'the packets being immiscible with ""d aqueous colloidal binder.

7. thod of making mixed packet photographic s mixn a non-diltusingcolore of reacting with the oxida- J aromatic amino developing agent onphotographic cu, elo ment, with a substantially *r-insoluole solvent forcolor-forming compound to orm a soiut n of the color-forming compound inthe solvent, u" ersing the solution in a gelatino-silver halide emulsionsensitive to at least one region but less than all regions of thevisible spectrum, mixing said dispersion with frorut 2 parts of thesodium sa thacryiic acid copolyrner, persion and polymer SiG'fi/i on ofa polymeric car oxyi groups form a dlSl rsion e to at least one regionbut less of the visible spectrum, mixing said dis- "Ct LIIUTT'Z t ofmethyl-methacrylate thacrylic acid coadding he .nixture of di persionand polyy and w "tirringa solution of styrene interxyl roups on thepolymeric chain, to form at. spe s of gelatin, interpolymer and silverhalide .ainingthc color-forming compound, the same way saidlastmentioned dispersion, at least one other dispersion of particles ofgelatin,

interpolymer, different non-dillusing color-forming compound ant ilver"lide sensitive to a region of the visible spect 1, di rent from that towhich firstsilver halide is sensitive, in each of said disd copolymcrbeing used in an amount from about 2 times the am int of gelatin, andsaid interpolymers being used in than onehalf the amount of g n, andmixing said dispersions solution.

'xed packet photographic g a non-diffusing coloring with theoxidadeveloping ubstantially o,- rming compound to form a solution. oithe color-forming compound in the solvent, disp rs ng the solulino-silver is: emulsion sen it less g said dis- ,rts of the emoth/acrylic acid conixture of dispersion and polyh stirring solution ofinterpolymer an u,/-unsaturated carboxylic acid to 1 Suki sod :1 salt ofne'r, adding to slowly a d of styrene a form dim of "rticles of gelatin,interpolymer and silver contai the color-forming compound,

forming in the same may as said last-mentioned dispersion, at least oneother dispersion of particles of gelatin, interpolymer, differentnon-diffusing color-forming compound and silver halide sensitive to aregion of the visible spectrum diiferent from that to which saidfirstmentioned silver halide is sensitive, in each of said dispersionssaid water-soluble polymer being used in an amount from about 1 to about2 times the amount of gelatin, and said interpolymer being used in anamount less than one-half the amount of gelatin, and mixing saiddispersions of particles with a gelatin solution.

10. A light-sensitive mixed packet photographic emulsion comprisingpackets or discrete particles of gelatin reacted with a water-solublesalt of an interpolymer of styrene, said interpolymer containing atleast a carboxylic acid group of the groups selected from the classconsisting of carboxylic acid and carboxylic acid amide groups, saidparticles or packets containing a non-diffusing colorforming compoundcapable of reacting with the oxidation product of a primary aromaticamino developing agent on photographic development, and silver halidesensitive to at least one region but less than all regions of thevisible spectrum, and at least one separate set of packets or discreteparticles of gelatin reacted with said interpolymer, containing anon-diffusing color-forming compound difierent from said first-mentionedcolor-forming compound and silver halide sensitive to a region of thevisible spectrum different from that to which said first-mentionedsilver halide is sensitive, the sensitive and color-forming ingredientsbeing within the respective packets or discrete particles and all ofsaid packets or discrete particles being dispersed in gelatin and havingmixed therewith the sodium salt of methylmethacrylate-methacrylic acidcopolymer.

11. A light-sensitive mixed packet photographic emulsion comprisingpackets or discrete particles of gelatin reacted with the ammonium saltof styrene-acrylamideacrylic acid interpolymer, said particles orpackets containing a non-difiusing color-forming compound capable ofreacting with the oxidation product of a primary aromatic aminodeveloping agent on photographic development, and silver halidesensitive to at least one region but less than all regions of thevisible spectrum, and at least one separate set of packets or discreteparticles of gelatin reacted with said interpolymer, containing anon-diffusing color-forming compound diflrerent from saidfirst-mentioned color-forming compound and silver halide sensitive to aregion of the visible spectrum difierent from that to which saidfirst-mentioned silver halide is sensitive, the sensitive andcolor-forming ingredients being within the respective packets ordiscrete particles and all of said packets or discrete particles beingdispersed in gelatin and having mixed therewith the sodium salt ofmethylmethacrylate-methacrylic acid copolymer.

References Cited in the file of this patent UNITED STATES PATENTS1,976,679 Fikentscher Oct. 9, 1934 2,284,877 Martinez June 2, 19422,399,084 Watson Apr. 23, 1946 2,490,749 Fierke et al Dec. 6, 19492,548,526 Godowsky Apr. 10, 1951 2,565,418 Yackel Aug. 21, 1951

1. A LIGHT-SENSITIVE MIXED PACKET PHOTOGRAPHIC EMULSION COMPRISINGPACKETS OR DISCRETE PARTICLES OF GELATIN REACTED WITH A WATER-SOLUBLESALT OF AN INTERPOLYMER OF STYRENE AND AN A,B-UNSATURATED CARBOXYLICACID, SAID PARTICLES OR PACKETS CONTAINING A NON-DIFFUSING COLOR-FORMINGCOMPOUND CAPABLE OF REACTING WITH THE OXIDATION PRODUCT OF A PRIMARYAROMATIC AMINO DEVELOPING AGENT ON PHOTOGRAPHIC DEVELOPMENT, AND SILVERHALIDE SENSITIVE TO AT LEAST ONE REGION BUT LESS THAN ALL REGIONS OF THEVISIBLE SPECTRUM, AND AT LEAST ONE SEPARATE SET OF PACKETS OR DISCRETEPARTICLES OF GELATIN REACTED WITH SAID INTERPOLYMER CONTAINING ANON-DIFFUSING COLOR-FORMING COMPOUND DIFFERENT FROM SAID FIRST MENTIONEDCOLOR-FORMING COMPOUND AND SILVER HALIDE SENSITIVE TO A REGION OF THEVISIBLE SPECTRUM DIFFERENT FROM THAT TO WHICH SAID FIRST MENTIONEDSILVER HALIDE IS SENSITIVE, THE SENSITIVE AND COLOR-FORMING INGREDIENTSBEING WITHIN THE RESPECTIVE PACKETS OR DISCRETE PARTICLES AND ALL OFSAID PACKETS OR DISCRETE PARTICLES BEING DISPERSED IN GELATIN HAVINGMIXED THEREWITH A WATERSOLUBLE SALT OF A POLYMER SELECTED FROM THE CLASSCONSISTING OF METHYLMETHACRYLATE-METHACRYLIC ACID COPOLYMER, ALGIN,CARBOXY METHYL CELLULOSE AND CELLULOSE SULFATE.